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Title:
RESINS FROM N-ALKENYL AMIDES AND ALLYLIC MONOMERS
Document Type and Number:
WIPO Patent Application WO/1999/019374
Kind Code:
A1
Abstract:
Copolymer resins derived from N-alkenyl amides, allylic monomers, and optionally, ethylenic monomers are disclosed. The resins are easily produced without need for reaction solvents to control rate of polymerization and without need for chain-transfer agents to limit molecular weight. The resins are useful in coatings, inks, adhesives, elastomers, foams, surfactants, plasticizers, and polymer composites.

Inventors:
Guo, Shao-hua (1109 Greenhill Road, West Goshen, PA, 19380, US)
Adamchuk, Mark R. (932 Oakbourne Road, West Chester, PA, 19382, US)
Kesling Jr., Haven S. (248 Friendship Road, Drexel Hill, PA, 19026, US)
Braunstein, David M. (540 Greenhill Lane, Berwyn, PA, 19314, US)
Application Number:
PCT/EP1998/006061
Publication Date:
April 22, 1999
Filing Date:
September 23, 1998
Export Citation:
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Assignee:
ARCO CHEMICAL TECHNOLOGY, L.P. (Two Greenville Crossing, Suite 238 4001 Kennett Pik, Greenville DE, 19807, US)
ARCO CHEMIE TECHNOLOGIE NEDERLAND B.V. (Theemsweg 14, P.O. Box 7195, HD Rotterdam, NL-3000, NL)
International Classes:
C08F216/20; C08F218/12; C08F226/00; (IPC1-7): C08F216/14; C08F226/00
Foreign References:
US5382642A
US5475073A
US3149091A
Attorney, Agent or Firm:
Smaggasgale, Gillian Helen (Mathys & Squire, 100 Grays Inn Road, London WC1X 8AL, GB)
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Claims:
We claim:
1. A resin which comprises recurring units of: (a) an Nalkenyl amide; (b) one or more allylic monomers selected from the group consisting of allyl esters, allyl ethers, and alkoxylated allylic alcools; and (c) optionally, one or more ethylenic monomers selected from the group consisting of vinyl aromatic monomers, acrylates and methacrylates, unsaturated nitriles, vinyl esters, vinyl ethers, vinyl halides, vinylidene halides, unsaturated anhydrides, unsaturated dicarboxylic acids, allylic alcools, acrylic and methacrylic acids, acrylamide and methacrylamide, fluoroalkyl acrylates and methacrylates, and conjugated dienes.
2. The resin of claim 1 wherein the Nalkenyl amide is an Nvinyl lactam.
3. The resin of claim 2 wherein the Nvinyllactam is selected from the group consisting of Nvinylpyrrolidone and Nvinylcaprolactam.
4. The resin of claim 1 comprising recurring units of an alkoxylated allyl alcool of the formula CH2=CHCH2 (A) nOH in which A is an oxyalkylene group, and n, which is the average number of oxyalkylene groups, has a value within the range of 1 to 50.
5. The resin of claim 1 comprising from about 5 to about 95 wt. % of the Nalkenyl amide, and from about 5 to about 95 wt. % of the allylic monomer.
6. The resin of claim 1 comprising from about 1 to about 50 wt. % of the ethylenic monomer.
7. The resin of claim 1 having a number average molecular weight within the range of about 500 to about 100,000.
8. The resin of claim 1 having an average hydroxyl functionality within the range of 0 to 20.
9. The resin of claim 1 having a glasstransition temperature within the range of about50°C to about 100°C.
10. The resin of claim 1 having a hydroxyl number within the range of about 0 mg KOH/g to about 500 mg KOH/g.
11. The resin of claim 1 having an average hydroxyl functionality within the range of 2 to 10, a number average molecular weight within the range of about 500 to about 10,000, and a hydroxyl number within the range of about 20 to about 500.
12. A thermoset coating, sealant, elastomer, adhesive, or foam which comprises the rection product of: (a) the resin of claim 11; and (b) a member selected from the group consisting of: (1) a melamine resin, to produce a melamine thermoset; (2) a dior polyisocyanate or an isocyanateterminated prepolymer, to produce a polyurethane; (3) an epoxy resin, to produce an epoxy thermoset; (4) an anhydride, to produce a thermoset polyester; (5) a fatty acid and a lowmolecularweight polyol, to produce an alkyd; and (6) a fatty acid, a lowmolecularweight polyol, and a di or polyisocyanate, to produce a polyurethane modifie alkyd.
13. A resin which comprises recurring units of: (a) an Nvinyllactam; (b) a propoxylated allyl alcohol of the formula CH2=CHCH2 (A) nOH in which A is an oxypropylene group, and n, which is the average number of oxypropylene groups, has a value within the range of 1 to 50; and (c) optionally, one or more ethylenic monomers selected from the group consisting of vinyl aromatic monomers, acrylates and methacrylates, unsaturated nitriles, vinyl esters, vinyl ethers, vinyl halides, vinylidene halides, unsaturated anhydrides, unsaturated dicarboxylic acids, allylic alcools, acrylic and methacrylic acids, acrylamide and methacrylamide, fluoroalkyl acrylates and methacrylates, and conjugated dienes.
14. The resin of claim 13 comprising from about 5 to about 95 wt. % of the Nvinyllactam, and from about 5 to about 95 wt. % of the propoxylated allyl alcool.
15. The resin of claim 14 wherein the Nvinyllactam is Nvinyl pyrrolidone.
16. The resin of claim 13 having an average hydroxyl functionality within the range of 2 to 10, a number average molecular weight within the range of about 500 to about 10,000, and a hydroxyl number within the range of about 20 mg KOH/g to about 500 mg KOH/g.
17. A process which comprises copolymerizing an Nalkenyl amide with an allylic monomer selected from the group consisting of allyl esters, allyl ethers, and alkoxylated allylic alcools in the presence of a freeradical initiator.
18. The process of claim 17 performed at a temperature within the range of about 90°C to about 200°C.
19. The process of claim 17 wherein the Nalkenyl amide is an N yinyllactam.
20. The process of claim 19 wherein the Nvinyllactam is selected from the group consisting of Nvinylpyrrolidone and Nvinylcaprolactam.
21. The process of claim 17 wherein the allylic monomer is a propoxylated allyl alcohol of the formula CH2=CHCH2 (A) nOH in which A is an oxypropylene group, and n, which is the average number of oxypropylene groups, has a value within the range of 1 to 50.
22. The process of claim 17 wherein the resin has an average hydroxyl functionality within the range of 2 to 10, a number average molecular weight within the range of about 500 to about 10,000, and a hydroxyl number within the range of about 20 to about 500.
23. A resin which comprises recurring units of: (a) an acrylatefunctionalized pyrrolidone; (b) one or more allylic monomers selected from the group consisting of allyl esters, allyl ethers, and alkoxylated allylic alcools; and (c) optionally, one or more ethylenic monomers selected from the group consisting of vinyl aromatic monomers, acrylates and methacrylates, unsaturated nitriles, vinyl esters, vinyl ethers, vinyl halides, vinylidene halides, unsaturated anhydrides, unsaturated dicarboxylic acids, ållylic alcohols, acrylic and methacrylic acids, acrylamide and methacrylamide, fluoroalkyl acrylates and methacrylates, and conjugated dienes.
24. The resin of claim 23 wherein the acrylatefunctionalized pyrrolidone is an acrylate ester derived from an N2hydroxyalkyl pyrrolidone.
25. The resin of claim 23 wherein the acrylatefunctionalized pyrrolidone is an acrylate ester derived from an Npolyether pyrrolidone.
Description:
RESINS FROM N-ALKENYL AMIDES AND ALLYLIC MONOMERS FIELD OF THE INVENTION The invention relates to copolymer resins derived from N-alkenyl amides and aliylic monomers. The resins are useful in many applications, including coatings, inks, adhesives, elastomers, foams, surfactants, plasticizers, and polymer composites.

BACKGROUND OF THE INVENTION Copolymers derived from allylic monomers such as allyl alcool, allyl esters, and alkoxylated allylic alcools are valable for coatings, inks, adhesives, and other thermosets. For example, copolymers of allyl alcohol or propoxylated allyl alcools with styrene (see, e. g., U. S. Pat. Nos.

5,382,642 and 5,451,631), allyl esters (e. g., U. S. Pat. Nos. 5,480,954 and 5,543,483), or acrylates (e. g., U. S. Pat. Nos. 5,475,073 and 5,525,693) are relatively low molecular weight resins that are useful for melamine, polyurethane, and alkyd coatings. Copolymer resins from allylic monomers are generally quite. soluble in organic solvents, but are not very soluble in water. Water solubility is often imparted to the resins by incorporating an acid-functional monomer such as acrylic or methacrylic acid. Neutralization of the resin with a base enhances its water solubility. Unfortunately, undesirably large amounts of acrylic acids are often needed for adequate water solubility of the resin. In addition, neutralization of resins, while improving water solubility, can adversely impact coating appearance and resistance of the coating to staining and moisture.

N-alkenyl amides, particularly N-vinyl-lactams such as N-vinyl- pyrrolidone and N-vinylcaprolactam, homopolymerize to give water-soluble polymers that are valable for cosmetics, dispersants, flocculants, paper- making chemicals, textiles, pharmaceuticals, and polymer composites. In polymer composites, for example, poly (N-vinylpyrrolidone) can be used as

an intercalant polymer for making nanocomposites, which comprise a thermoplastic or thermoset matrix polymer, a layered inorganic material such as a clay, and the intercalant polymer. The poly (N-vinylpyrrolidone) penetrates the layers of inorganic material and helps it exfoliate when combine with the matrix polymer. Because poly (N-vinylpyrrolidone) is relatively expensive, however, alternative intercalant polymers are of interest.

New copolymer resins are needed. Preferably, the resins would offer a less-expensive alternative to the N-alkenyl amide resins now available.

Preferably, the resins would offer the avantages of allylic resins (such as hydroxyl functionality), but would have greater hydrophilicity and would give coatings with improved appearance and physical properties. Ideally, the copolymer resins would be valable in a wide variety of applications, including coatings, inks, adhesives, elastomers, foams, and polymer composites.

SUMMARY OF THE INVENTION The invention is a copolymer resin. The resin comprises recurring units of an N-alkenyl amide and one or more allylic monomers selected from allyl esters, allyl ethers, and alkoxylated allylic alcools. Optionally, the resin inclues recurring units of one or more other ethylenic monomers. The resins are easily produced without need for rection solvents to control rate of polymerization and without need for chain-transfer agents to limit molecular weight.

Resins of the invention offer valable avantages for thermoset coatings, sealants, elastomers, adhesives, and foams, as well as for composite materials made using the resins. In composites, the resins offer good performance in a less-expensive alternative to commercially available intercalants such as poly (N-vinylpyrrolidone). In coatings and other

thermoset applications, the resins offer oil resistance, enhanced hydrophilicity, and a reduced dependence on salt content for water solubility.

DETAILED DESCRIPTION OF THE INVENTION Copolymer resins of the invention comprise recurring units of an N- alkenyl amide, an allylic monomer, and optionally, an ethylenic monomer.

N-alkenyl amides useful in the invention are compound that have a substituted or unsubstituted carbon-carbon double bond attache directly to nitrogen of an amide. Preferred N-alkenyl amides have the general structure: R,- (C=O)-NR2-C (R3) =C (R4) RS in which each of R,, R2, R3, R4, and Rs separately represents a member selected from the group consisting of hydrogen and Cl-C, alkyl. R, and R2may form a ring to give an alkenyl- lactam. Suitable alkenyl amides inclue, for example, N-vinylformamide, N- vinyl-N-methylacetamide, N-vinyl-N-methylpropanamide, and the like, and mixtures thereof. Other suitable N-alkenyl amides are described in U. S. Pat.

Nos. 5,622,533 and 5,625,076. the teachings of which are incorporated herein by reference.

Preferred N-alkenyl amides include N-vinyl-lactams, which are cyclic amides that have a vinyl group (CH2=CH-) attache to the nitrogen atom of the amide moiety. The lactam preferably has from 4 to 10 ring atoms. More preferably, the lactam has from 5 to 7 ring atoms. Suitable N-vinyl-lactams inclue, for example, N-vinylpropiolactam, N-vinylpyrrolidone, N-vinyl- valerolactam, N-vinylcaprolactam, and the like, and mixtures thereof.

N-vinylpyrrolidone and N-vinylcaprolactam are particularly preferred.

In addition to or in place of the N-alkenyl amide, resins of the invention can incorporate recurring units of an acrylate-functionalized pyrrolidone. Suitable acrylate-functionalized pyrrolidones include ester rection products of N-2-hydroxyalkylpyrrolidones and acrylic or methacrylic acid. Suitable acrylate-functionalized pyrrolidones also include ester rection products of N-polyether pyrrolidones and acrylic or methacrylic acid.

Examples of these and other useful acrylate-functionalized pyrrolidones appear in U. S. Pat. No. 5,629,359, the teachings of which are incorporated herein by reference.

Copolymer resins of the invention incorporate one or more allylic monomers. Suitable allylic monomers include allyl esters, allyl ethers, and alkoxylated allylic alcools.

Allyl esters suitable in the invention preferably have the general structure: CH2=CR'-CH2-O-CO-R in which R is hydrogen or a saturated or unsaturated linear, branche, or cyclic C,-C30 alkyl, aryl, or aralkyl group, and R'is selected from the group consisting of hydrogen and C,-CS alkyl.

Suitable allyl esters inclue, for example, allyl formate, allyl acetate, allyl butyrate, allyl benzoate, methallyl acetate, allyl fatty esters, and the like, and mixtures thereof. Particularly preferred are allyl esters derived from allyl alcohol and methallyl alcool. Most preferred are C,-Cs alkyl esters of alla ! alcool and methallyl alcool.

Preferred allyl ethers have the general structure: CH2=CR'-CH2-O-R in which R is a saturated linear, branche, or cyclic Cl-C30 alkyl, aryl, or aralkyl group, and R'is selected from the group consisting of hydrogen and C,-Cs alkyl. Suitable allyl ethers inclue, for example, allyl methyl ether, allyl ethyl ether, allyl tert-butyl ether, allyl methylbenzyl ether, and the like, and mixtures thereof.

The copolymer resin can incorporate recurring units of an alkoxylated allylic alcool. Preferred alkoxylated allylic alcools have the general structure CH2=CR'-CH2 (A) nOH in which A is an oxyalkylene group, R' is selected from the group consisting of hydrogen and C,-CS alkyl, and n, which is the average number of oxyalkylene groups in the alkoxylated allylic alcool, has a value from 1 to 50. Preferred oxyalkylene groups are oxyethylene, oxypropylene, oxybutylenes, and mixtures thereof. Most

preferred are propoxylated allylic alcools having an average of 1 to 10 oxypropylene groups.

Suitabie alkoxylated allylic alcools can be prepared by reacting an allylic alcohol with up to about 50 equivalents of one or more alkylene oxides in the presence of a basic catalyst as described, for example, in U. S. Pat.

Nos. 3,268,561 and 4,618,703, the teachings of which are incorporated herein by reference. As will be apparent to those skilled in the art, suitable alkoxylated allylic alcools can also be made by acid catalysis, as described, for example, in J. Am. Chem. Soc. 71 (1949) 1152.

The relative amounts of N-alkenyl amide and allylic monomer used to make copolymer resins of the invention depends on many factors, including the desired degree of hydrophilicity, the desired hydroxyl content, the nature of the monomers used, suitability for the particular end-use application, and other factors. Preferably, the copolymer resin comprises from about 5 to about 95 wt. % of N-alkenyl amide recurring units, and from about 5 to about 95 wt. % of allylic monomer recurring units. More preferably, the resin comprises from about 25 to about 75 wt. % of N-alkenyl amide recurring units, and from about 25 to about 75 wt. % of allylic monomer recurring units. Most preferred resins comprise from about 30 to about 60 wt. % of N-alkenyl amide recurring units, and from about 40 to about 70 wt. % of allylic monomer recurring units.

Optionally, the copolymer resin incorporates recurring units derived from one or more ethylenic monomers. The ethylenic monomer is often included to control resin solubility, enhance physical properties, or reduce cost. Preferably, the ethylenic monomer is used in an amount within the range of about 0.1 to about 50 wt. %. A more preferred range is from about 1 to about 25 wt. %. Preferred ethylenic monomers inclue, for example, vinyl aromatic monomers, acrylates and methacrylates, unsaturated nitriles, vinyl esters, vinyl ethers, vinyl halides, vinylidene halides, unsaturated

anhydrides, unsaturated dicarboxylic acids, allylic alcools, acrylic and methacrylic acids, acrylamide and methacrylamide, fluoroalkyl acrylates and methacrylates, conjugated dienes, and the like, and mixtures thereof.

The copolymer resins of the invention preferably have number average molecular weights within the range of about 500 to about 100,000.

A more preferred range is from about 2500 to about 50,000.

The copolymer resins have hydroxyl numbers within the range of 0 to about 400 mg KOH/g. (In other words, the resins need not have any hydroxyl group content, but may incorporate a substantial proportion of hydroxyl groups.) A more preferred range for the hydroxyl number is from about 25 to about 250 mg KOH/g; most preferred is the range from about 50 to about 200 mg KOH/g. The need for hydroxyl groups depends on the intended end-use application. In coatings, for example, it is often important for the resin to have a significant hydroxyl group content; in contrast, many composites can benefit from copolymer resins of the invention that contain no hydroxyl groups.

The average hydroxyl functionality of the copolymer resins generally ranges from 0 to about 20. Preferably, the hydroxyl functionality is within the range of about 2 to about 20; most preferred is the range from about 3 to about 10. As noted above, the need for hydroxyl functionality depends on the desired end use.

In coating applications, glass-transition temperature of the copolymer resin can be important. Copolymer resins of the invention preferably have a glass-transition temperature (Tg) within the range of about-50°C to about 100°C. A more preferred range is from about-40°C to about 40°C.

The invention inclues a process for making the copolymer resins.

The process comprises copolymerizing an N-alkenyl amide with an allylic monomer selected from the group consisting of allyl esters, allyl ethers, and alkoxylated allylic alcools in the presence of a free-radical initiator.

The free-radical initiator is preferably a peroxide, hydroperoxide, or azo compound. Preferred initiators have a decomposition temperature greater than about 100°C. Examples include tert-butyl hydroperoxide, di- tert-butyl peroxide, tert-butyl perbenzoate, cumene hydroperoxide, and the like.

The amount of free-radical initiator needed varies, but is generally within the range of about 0.1 to about 10 wt. % based on the amount of monomers. Preferably, the amount of free-radical initiator used is within the range of about 1 to about 5 wt. %; most preferred is the range from about 2 to about 4 wt. %.

Generally, it is preferred to add the free-radical initiator to the reactor gradually during the course of the polymerization. When preparing coating resins, it is also desirable to add the N-alkenyl amide gradually to the reactor, and to match the addition rate of the free-radical initiator to the polymerization rate of the N-alkenyl amide. When an ethylenic monomer is included, it is preferred to add it in proportion to the N-alkenyl amide. For example, if half of the N-alkenyl amide is added gradually, then it is preferred to charge half of the ethylenic monomer initially and add the remaining portion with the N-alkenyl amide. As with the N-alkenyl amide, all of the ethylenic monomer can be added gradually. These techniques produce a polymer that has an evenly distributed hydroxyl functionality that is relatively independent of molecular weight.

A batch process in which all of the monomers are charged initially to the reactor is suitable when the goal is to make copolymer resins for applications in which the distribution of hydroxyl functionality in the resin is less important. In the preferred batch process, the N-alkenyl amide and allylic monomer are charged initially and the free-radical initiator is added gradually as the rection proceeds.

The process of the invention can be performed over a wide temperature range. Generally, the rection temperature will be within the

range of about 60°C to about 300°C. A more preferred range is from about 90°C to about 200°C; most preferred is the range from about 1 00°C to about 180°C.

The process of the invention is advantageously performed in the absence of any rection solvent, but a solvent may be included if desired.

Useful solvents include those that will not interfere with the free-radical polymerization rection or otherwise react with the monomers. Suitable solvents inclue, for example, ethers, esters, ketones, aromatic and aliphatic hydrocarbons, alcools, glycol ethers, glycol ether esters, and the like, and mixtures thereof.

An avantage of the process of the invention is that no solvent is needed to polymerize reactive monomers at a low rate of polymerization.

This obviates the need to remove a solvent later from the resin and saves on the expense of using and recovering a solvent. The process also gives low molecular weight polymers useful as polymer intermediates without the need to include a chain-transfer agent. Chain-transfer agents often impart undesirable odors and detract from a polymer's ultimate physical properties.

The invention inclues thermoset coatings, sealants, elastomers, adhesives, and foams made using hydroxy-functional copolymer resins of the invention. The thermosets include melamines, polyurethanes, epoxy thermosets, polyesters, alkyds, and uralkyds. For example, melamine- based polymers, especially coatings, can be prepared by reacting the copolymer resins with melamine resins. Suitable melamine resins include commercial grade hexamethoxymethylmelamines, such as, for example, CYMEL 303 crosslinking agent, a product of Cytec.

A polyurethane composition is made by reacting a hydroxy-functional copolymer resin of the invention with a di-or polyisocyanate or an isocyanate-terminated prepolymer. Prepolymers derived from the copolymer resins of the invention can be used. Optionally, a low molecular weight

chain extender (dol, diamine, or the like) is included. Suitable di-or polyisocyanates are those well known in the polyurethane industry, and inclue, for example, toluene diisocyanate, MDI, polymeric MDls, carbodiimide-modified Midis, hydrogenated Midis, isophorone diisocyanate, 1,6-hexanediisocyanate, and the like. Isocyanate-terminated prepolymers are made in the usual way from a polyisocyanate and a polyether polyol, polyester polyol, or the like. The polyurethane is formulated at any desired NCO index, but it is preferred to use an NCO index close to 1. If desired, all of the available NCO groups are reacted with hydroxy groups from the copolymer resin and any chain extenders. Alternatively, an excess of NCO groups remain in the product, as in a moisture-cured polyurethane. Many types of polyurethane products can be made, including, for example, adhesives, sealants, coatings, and elastomers. Other suitable methods for making polyurethane compositions are described in U. S. Pat. No. 2,965,615, the teachings of which are incorporated herein by reference.

The invention inclues epoxy thermosets, which are the rection products of hydroxy-functional copolymer resins of the invention and an epoxy resin. Suitable epoxy resins generally have two or more epoxy groups available for rection with the hydroxyl groups of the copolymer resin. Particularly preferred epoxy resins are bisphenol-A diglycidyl ether and the like. Other suitable methods for making epoxy thermosets are described in U. S. Pat. No. 4,609,717, the teachings of which are incorporated herein by reference.

The invention inclues thermoset polyesters that are the rection products of hydroxy-functional copolymer resins of the invention and an anhydride or a di-or polycarboxylic acid. Suitable anhydrides and carboxylic acids are those commonly used in the polyester industry.

Examples include phthalic anhydride, phthalic acid, maleic anhydride, maleic acid, adipic acid, isophthalic acid, terephthalic acid, sebacic acid, succinic

acid, trimellitic anhydride, and the like, and mixtures thereof. Other suitable methods for making thermoset polyesters are described in U. S. Pat. No.

3,457,324, the teachings of which are incorporated herein by reference.

The invention inclues alkyd compositions prepared by reacting a hydroxy-functional copolymer resin of the invention with an unsaturated fatty acid. Suitable unsaturated fatty acids are those known in the art as useful for alkyd resins, and inclue, for example, oleic acid, ricinoleic acid, linoleic acid, licanic acid, and the like, and mixtures thereof. Mixtures of unsaturated fatty acids and saturated fatty acids such as lauric acid or palmitic acid can also be used. The alkyd resins are particularly useful for making alkyd coatings. For exampie, a hydroxy-functional copolymer resin, or a mixture of the resin and glycerin or another low molecular weight polyol, is first partially esterified with an unsaturated fatty acid to give an alkyd resin. The resin is then combine with an organic solvent, and the resin solution is stored until needed. A drying agent such as cobalt acetate is added to the solution of alkyd resin, the solution is spread onto a surface, the solvent evaporates, and the resin cures leaving an alkyd coating of the invention.

Other suitable methods for making alkyd resins and coatings are described in U. S. Pat. No. 3,423,341, the teachings of which are incorporated herein by reference.

Instead of combining the alkyd resin with an organic solvent, the resin can be disperse in water to make a water-based alkyd coating formulation.

To improve the water dispersability of the alkyd rein, a free hydroxyl group in the alkyd resin can be converted to a salt. For example, the alkyd resin can be reacted with phthalic anhydride to give a resin that contains phthalic acid residues; addition of sodium hydroxide makes the sodium phthalate salt, and provides a water-dispersable alkyd resin derived from the allyl ester copolymer. See, for example, U. S. Pat. No. 3,483,152.

The invention inclues polyurethane-modified alkyds (uralkyds) prepared from hydroxy-functional copolymer resins of the invention. These uralkyd resins are especially valable for making uralkyd coatings. The hydroxy-functional copolymer resin is first partially esterified with an unsaturated fatty acid (described above) to give an alkyd resin. The alkyd resin, which contains some free hydroxyl groups, is reacted with a di-or polyisocyanate (described above) to give a prepolymer. The prepolymer is then reacted with a chain extender, atmospheric moisture, or additional alkyd resin to give a uralkyd coating. Other s. uitable methods for making uralkyd resins and coatings are described in U. S. Pat. No. 3,267,058, the teachings of which are incorporated herein by reference.

Resins of the invention offer valable avantages for thermosets, including coatings, sealants, elastomers, adhesives, and foams. In coatings, the resins offer oil resistance, enhanced hydrophilicity, and a reduced dependence on salt content for water solubility : These improvements are obtained while maintaining desirable coating appearance and physical properties.

In composites, the resins offer good performance in a less-expensive alternative to commercially available intercalants such as poly (N-vinyl- pyrrolidone). Incorporation of allylic monomers allows formulators to control performance of the intercalant polymer, including bonding efficiency, while minimizing cost.

The following examples merely illustrate the invention. Those skilled in the art will recognize many variations that are within the spirit of the invention and scope of the claims.

EXAMPLE 1 Copolymer Resin from N-Vinylpyrrolidone and Propoxylated Allyl Alcohol Allyl alcohol propoxylate (average of 1.6 oxypropylene units, 350 g) is charged to a one-liter rection kettle equipped with agitato, heating

mantle, temperature controller, nitrogen purge device, condenser, and addition pump. N-vinylpyrrolidone (350 g) and t-butyl perbenzoate (10 g) are mixed at 5°C in a chialer, deoxygenated with nitrogen, and charged to the addition pump. After purging the reactor three times with nitrogen, the reactor contents are heated to 145°C. The N-vinyipyrrolidone/initiator mixture is gradually added at an even rate to the reactor over 4 h at 145°C.

The mixture is heated for another 45 min. following completion of the monomer addition. Unreacted monomers are removed by vacuum stripping of the mixture at 160°C. The copolymer resin product has Mw = 12,600; Mn = 3260; and Tg = 21°C.

EXAMPLE 2 Copolymer Resin from N-Vinylpyrrolidone and Propoxylated Allyl Alcohol The procedure of Example 1 is followed, but allyl alcohol propoxylate having an average of ten oxypropylene units (350 g) is used. The polymer has T9 =-28°C.

EXAMPLE 3 Copolymer Resin from N-Vinylpyrrolidone and Propoxylated Allyl Alcohol The procedure of Example 1 is followed using 525 g of allyl alcohol propoxylate (ave. of 1.6 oxypropylene units) and 175 g of N-vinylpyrrolidone.

The copolymer resin has Mw = 8660; Mn = 1570; and hydroxyl number = 172 mg KOH/g.

EXAMPLE 4 Copolymer Resin from N-Vinylpyrrolidone, Propoxylated Allyl Alcool, and Allyl Alcohol Allyl alcohol (375 g), allyl alcohol propoxylate (ave. of 1.6 oxypropylene units, 375 g), and N-vinylpyrrolidone (750 g) are charged to a five-liter rection ketle equipped with agitato, heating mantle, temperature

controller, inlets for nitrogen and vacuum, condenser, and addition pump.

Di-tert-butyl peroxide (25 g) is charged to the reactor. Additional di-tert-butyl peroxide (50 g) is added to the addition pump. After purging the reactor three times with nitrogen, the reactor contents are heated to 135°C. The initiator is gradually added at a decreasing rate to the reactor over 4 h at 1350C. The initiator addition is performed as follows: first hour, 20 g; second hour, 15 g; third hour, 10 g; fourth hour 5 g. The mixture is heated for another 60 min. following completion of the monomer addition. Unreacted monomers are removed by vacuum stripping of the mixture at 160°C.

The preceding examples are meant only as illustrations; the following claims define the scope of the invention.